This application is the U.S. national-phase application of PCT International Application No. PCT/GB99/00744.
This invention relates to the catalytic generation of hydrogen.
Hydrogen is currently used mainly in industry, in activities such as the manufacture of fertilisers, petroleum processing, methanol synthesis, annealing of metals and producing electronic materials. In the foreseeable future, the emergence of fuel cell technology will extend the use of hydrogen to domestic and vehicle applications.
A fuel cell works best when the anode is supplied with neat hydrogen. In the design of practical systems, however, other factors also need to be considered, including the availability, cost, supply, distribution, storage and release of clean hydrogen. When all these factors are taken into consideration, alternative methods of fueling can show an overall advantage.
New fuel-processing technologies for generating hydrogen tend to be based either on steam-reforming or on partial oxidation. Each approach has its merits. Partial oxidation is a fast exothermic process, resulting in rapid start-up and short response times. Steam reforming is endothermic and very efficient, producing hydrogen from both the fuel and the steam.
However, our work on system simulations leads us to predict that, in terms of efficiency, the ideal fuel-processor is likely to function by a combination of partial oxidation and steam reforming. In our previous work, (see EP 0217532; EP 0262947; WO 96/00186 and Platinum Metals Review, 1989, 33 (3) 118-127), we have shown that the two reactions can be carried out simultaneously in the same catalyst bed using a catalytic hydrogen generator which has become known as the HotSpot(trademark) reactor. The process which takes place in the HotSpot reactor is a self-sustaining combination of exothermic partial oxidation and endothermic steam-reforming to produce a gas-stream containing mainly hydrogen, carbon dioxide and nitrogen, and is characterised by a low rate of carbon monoxide formation. WO 96/00186 teaches that the organic fuel can be an oxygenate, e.g. methanol.
Possibly, the easiest fuel to process is methanol. However, because of certain disadvantages of methanol, it is by no means certain that methanol will be widely adopted for fuel cell vehicle and domestic applications.
An object of the present invention is to provide an improved process for generating hydrogen by oxidatively reforming (ie by partial oxidation alone or with the combination of steam reforming) of an organic fuel.
According to the present invention there is provided a process for the catalytic gene ration of hydrogen by the self-starting, self-sustaining oxidation of an organic fuel wherein a mixture of the organic fuel and an oxygen-containing gas and optionally steam is contacted with a precious metal catalyst which is selective for the oxidative reforming of organic fuels characterised in that the organic fuel comprises dimethyl ether.
Preferably, steam is introduced into the mixture of dimethyl ether and oxygen-containing gas after the self-starting, self-sustaining partial oxidation of the dimethyl ether has commenced.
Further preferably, the oxygen-containing gas is air.
A suitable catalyst for the process of the invention is platinum or rhodium supported on zirconia or a mixture of ceria and zirconia.
Preferably, platinum or rhodium comprises 0.1 weight % to 5 weight % of the total weight of the supported catalyst.
Further preferably, the weight ratio of ceria to zirconia in the catalyst support material is from 0.5 to 99.5 to 99.5 to 0.5.
The present invention is also the use in a fuel cell system of a process for the generation of hydrogen as defined herein.
An advantageous feature of the process of the present invention is that it provides for a highly compact and responsive fuel processing unit characterised by the absence of separate or integral shift reactors.
As an alternative to methanol, dimethyl ether (DME) has several further advantages, namely:
(i) it has much lower toxicity;
(ii) it is less hygroscopic, making it less corrosive;
(iii) it has a higher energy density; and
(iv) although a gas at ambient temperatures. it is easy to liquify.
Furthermore, as dimethyl ether has a high cetane number and combusts cleanly, it is being assessed as an alternative to conventional diesel fuel. Should this happen, it can be expected to become much more widely available than methanol.
Dimethyl ether can be used either as a fuel in its own right or as a promoter for liquified hydrocarbon fuels (eg LPG) that are more difficult to convert to hydrogen. The dimethyl ether promotes start-up from ambient temperature.